JP3193740B2 - Organosilicon compound and method for producing the same - Google Patents
Organosilicon compound and method for producing the sameInfo
- Publication number
- JP3193740B2 JP3193740B2 JP23553291A JP23553291A JP3193740B2 JP 3193740 B2 JP3193740 B2 JP 3193740B2 JP 23553291 A JP23553291 A JP 23553291A JP 23553291 A JP23553291 A JP 23553291A JP 3193740 B2 JP3193740 B2 JP 3193740B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- embedded image
- organosilicon compound
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 150000003961 organosilicon compounds Chemical class 0.000 title description 33
- 238000004519 manufacturing process Methods 0.000 title description 7
- 125000000524 functional group Chemical group 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 19
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- 238000007259 addition reaction Methods 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000000962 organic group Chemical group 0.000 claims description 6
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- 229910052697 platinum Inorganic materials 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- -1 N-cyclohexylamino group Chemical group 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 239000009719 polyimide resin Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000000051 modifying effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 150000003377 silicon compounds Chemical group 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KVXVHMMBCSGZFS-UHFFFAOYSA-N but-3-enyl-[but-3-enyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=CCC[Si](C)(C)O[Si](C)(C)CCC=C KVXVHMMBCSGZFS-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 239000013615 primer Substances 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規な有機ケイ素化合
物及びその製造方法に関し、詳しくは分子鎖片末端に２
個以上のケイ素原子結合有機官能基を有し、他方の分子
鎖末端に２個以上のケイ素原子結合加水分解性基を有す
る、有機ケイ素化合物及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organosilicon compound and a method for producing the same.
The present invention relates to an organosilicon compound having at least two silicon-bonded organic functional groups and having at least two silicon-bonded hydrolyzable groups at the other molecular chain terminal, and a method for producing the same.
【０００２】[0002]
【従来の技術】従来、ケイ素原子結合水素原子とケイ素
原子結合加水分解性基とを有する有機ケイ素化合物とし
ては、トリアルコキシシランが知られている。また、こ
のトリアルコキシシランの誘導体である３−アミノプロ
ピルトリエトキシシラン、３−グリシドキシプロピルト
リメトキシシラン、ビニルトリメトキシシラン等が知ら
れており、これらはシランカップリング剤と呼ばれ、有
機樹脂と無機物質との間に介在して、両者の相溶性、接
着性等を向上させるために有用とされ、各種有機樹脂の
物理特性改質用添加剤、接着剤、プライマーとして広く
使用されている。さらに、本発明者らは、先にシロキサ
ンスペーサーを有する新規な異種二官能性有機ケイ素化
合物を提案した（特願平３−２７９２０号）。しかしな
がら、シランカップリング剤およびこれらの有機ケイ素
化合物は、一分子中に２個以上の加水分解性基を含有し
ていても、有機官能基を１個しか含有していないため、
用途によってはその特性を十分発揮できなかった。例え
ばアミノ基含有トリアルコキシシランをポリイミド樹脂
の改質剤として使用した場合には、ポリイミド樹脂の末
端にしか加水分解性基を導入できず、十分な改質効果が
得られないという問題があった。2. Description of the Related Art Conventionally, trialkoxysilane has been known as an organosilicon compound having a silicon-bonded hydrogen atom and a silicon-bonded hydrolyzable group. Further, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, and the like, which are derivatives of the trialkoxysilane, are known. Interposed between the resin and the inorganic substance, it is useful for improving the compatibility of both, adhesion, etc., widely used as additives for modifying the physical properties of various organic resins, adhesives, primers I have. Furthermore, the present inventors have previously proposed a novel heterobifunctional organosilicon compound having a siloxane spacer (Japanese Patent Application No. 3-27920). However, even though the silane coupling agent and these organosilicon compounds contain two or more hydrolyzable groups in one molecule, they contain only one organic functional group,
Depending on the application, its properties could not be fully exhibited. For example, when amino group-containing trialkoxysilane is used as a modifier for a polyimide resin, a hydrolyzable group can be introduced only to the terminal of the polyimide resin, and there is a problem that a sufficient modifying effect cannot be obtained. .
【０００３】[0003]
【発明が解決しようとする課題】本発明者らは、上記の
問題点を解決すべく鋭意研究した結果、本発明に到達し
た。すなわち、本発明の目的は、一分子中に２個以上の
有機官能基と２個以上のケイ素原子結合加水分解性基と
を有する新規な有機ケイ素化合物及びその製造方法を提
供するにある。DISCLOSURE OF THE INVENTION The present inventors have made intensive studies to solve the above problems, and as a result, have reached the present invention. That is, an object of the present invention is to provide a novel organosilicon compound having two or more organic functional groups and two or more silicon-bonded hydrolyzable groups in one molecule, and a method for producing the same.
【０００４】[0004]
【課題を解決するための手段およびその作用】本発明
は、一般式：The present invention provides a compound represented by the following general formula:
【化４】 （式中、Ｒ1は脂肪族不飽和結合を含まない同一または
異種の一価炭化水素基、Ｒ2は二価炭化水素基、 Ａはア
ミノ基、エポキシ官能性有機基、ヒドロキシ基から選択
される有機官能基またはこれらの官能基の活性水素がト
リオルガノシリル基で置換された有機官能基、Ｘは加水
分解性基、ｎは０または１の整数、ｍは０から１００ま
での整数、ｐは０または１の整数を示す。）で表される
有機ケイ素化合物（I）及び、一般式：Embedded image (Wherein, R 1 is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, R 2 is a divalent hydrocarbon group, and A is an amino group, an epoxy-functional organic group, or a hydroxy group. An organic functional group or an organic functional group in which active hydrogens of these functional groups are substituted with a triorganosilyl group, X is a hydrolyzable group, n is an integer of 0 or 1, m is an integer of 0 to 100, p Represents an integer of 0 or 1.) and an organosilicon compound (I) represented by the general formula:
【化５】 （式中、Ｒ1、Ｒ2、Ｘ、ｎ、ｍ、ｐは前記に同じであ
る。）で表される有機ケイ素化合物（II）と、アミノ
基、エポキシ官能性有機基、ヒドロキシ基から選択され
る有機官能基を含有する脂肪族不飽和炭化水素化合物ま
たはこれらの有機官能基の活性水素がトリオルガノシリ
ル基で置換された脂肪族不飽和炭化水素化合物とを付加
反応させることを特徴とする、一般式：Embedded image (Wherein, R 1 , R 2 , X, n, m, and p are the same as described above), and an amino group, an epoxy-functional organic group, or a hydroxy group. Characterized in that an addition reaction of an aliphatic unsaturated hydrocarbon compound containing an organic functional group to be performed or an aliphatic unsaturated hydrocarbon compound in which active hydrogen of these organic functional groups is substituted with a triorganosilyl group is performed. , The general formula:
【化６】 （式中、Ｒ1、Ｒ2、Ａ、Ｘ、ｎ、ｍ、ｐは前記に同じで
ある。）で表される有機ケイ素化合物（I）の製造方法
に関する。Embedded image (Wherein, R 1 , R 2 , A, X, n, m, and p are the same as described above).
【０００５】以下、本発明を詳細に説明する。本発明の
有機ケイ素化合物は、一般式：Hereinafter, the present invention will be described in detail. The organosilicon compound of the present invention has the general formula:
【化７】 で示される。 上式中、Ｒ1は脂肪族不飽和結合を含まな
い同一または異種の一価炭化水素基であり、具体的には
メチル基、エチル基、プロピル基等のアルキル基；フェ
ニル基、トリル基、キシリル基等のアリール基；クロロ
メチル基、パーフルオロメチル基等の置換アルキル基等
が例示される。 Ｒ2は二価炭化水素基であり、具体的に
はメチレン基、エチレン基、プロピレン基、ブチレン基
等のアルキレン基が挙げられる。Ａはアミノ基、Ｎ（２
−アミノエチル）アミノ基、Ｎ−シクロヘキシルアミノ
基等のアミノ基； グリシドキシ基、３,４エポキシシク
ロヘキシル基等のエポキシ官能性有機基；ヒドロキシ基
から選択される有機官能基、またはこれらの活性水素が
トリオルガノシリル基で置換された基である。以下に有
機官能基Ａと上述のＲ2が結合した有機官能基の例を示
す。Embedded image Indicated by In the above formula, R 1 is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, and specifically, an alkyl group such as a methyl group, an ethyl group, and a propyl group; a phenyl group, a tolyl group, An aryl group such as a xylyl group; a substituted alkyl group such as a chloromethyl group and a perfluoromethyl group; R 2 is a divalent hydrocarbon group, specifically, an alkylene group such as a methylene group, an ethylene group, a propylene group, and a butylene group. A is an amino group, N (2
An amino group such as -aminoethyl) amino group or N-cyclohexylamino group; an epoxy-functional organic group such as glycidoxy group or 3,4 epoxycyclohexyl group; an organic functional group selected from hydroxy group, or active hydrogen thereof. This is a group substituted with a triorganosilyl group. Hereinafter, examples of the organic functional group in which the organic functional group A and the above-described R 2 are bonded are shown.
【化８】 Embedded image
【化９】 Embedded image
【化１０】 Embedded image
【化１１】 Embedded image
【化１２】 Embedded image
【化１３】 Embedded image
【化１４】 Embedded image
【化１５】 Embedded image
【化１６】 Embedded image
【化１７】 Embedded image
【化１８】 Ｘは加水分解性基であり、メトキシ基やエトキシ基のよ
うなアルコキシ基、アセトキシ基、オキシム基、アミド
基等が例示される。ｎは０または１の整数であり、ｎが
０の場合は３個の有機官能基を有する有機ケイ素化合物
であり、またｎが１の場合は２個の有機官能基を有する
有機ケイ素化合物となる。ここでｎの数値は本発明の特
徴をなすものであり、ｎが０または１の整数をとること
によって、本発明の有機ケイ素化合物は一分子中に２ま
たは３個のケイ素原子に結合した有機官能基を有する有
機ケイ素化合物を提供することができる。ｍは０から１
００までの整数であり、ｍが０のときは加水分解性基結
合ケイ素原子が直接Ｒ2に結合しており、ｍが１増加す
る毎にＲ2と加水分解性基結合ケイ素原子の間に、Ｒ1が
２個結合したシロキサン単位が１単位ずつ増加する。ｐ
は０または１の整数であり、ｐが０のときは３個の加水
分解性基を有する有機ケイ素化合物となり、またｐが１
のときは２個の加水分解性基を有する有機ケイ素化合物
となる。Embedded image X is a hydrolyzable group, and examples thereof include an alkoxy group such as a methoxy group and an ethoxy group, an acetoxy group, an oxime group, and an amide group. n is an integer of 0 or 1, and when n is 0, it is an organosilicon compound having three organic functional groups, and when n is 1, it is an organosilicon compound having two organic functional groups. . Here, the numerical value of n is a feature of the present invention, and when n is an integer of 0 or 1, the organosilicon compound of the present invention is an organic silicon compound bonded to two or three silicon atoms in one molecule. An organosilicon compound having a functional group can be provided. m is 0 to 1
00 is an integer between, m has hydrolyzable groups bonded silicon atom directly bonded to R 2 is 0, each time m is increased by one between R 2 and hydrolyzable groups bonded silicon atoms , R 1 is increased by one unit. p
Is an integer of 0 or 1, and when p is 0, it becomes an organosilicon compound having three hydrolyzable groups, and p is 1
In this case, the organic silicon compound has two hydrolyzable groups.
【０００６】以下に、本発明の有機ケイ素化合物の製造
方法を説明する。本発明の製造方法で使用される有機ケ
イ素化合物（II）は一般式：The method for producing the organosilicon compound of the present invention will be described below. The organosilicon compound (II) used in the production method of the present invention has a general formula:
【化１９】 で表される。上式中、Ｒ1、Ｒ2、Ｘ、ｎ、ｍ、ｐは前記
と同じである。ｎが０の場合はケイ素原子結合水素原子
を３個有する有機ケイ素化合物であり、ｎが１の場合は
ケイ素原子結合水素原子を２個有する有機ケイ素化合物
である。このような有機ケイ素化合物の合成ルートの一
例として以下のルートが挙げられる。Embedded image It is represented by In the above formula, R 1 , R 2 , X, n, m, and p are the same as described above. When n is 0, it is an organosilicon compound having three silicon-bonded hydrogen atoms, and when n is 1, it is an organosilicon compound having two silicon-bonded hydrogen atoms. The following route is mentioned as an example of a synthesis route of such an organosilicon compound.
【化２０】 Embedded image
【０００７】本発明において、有機ケイ素化合物（II）
と付加反応させる、アミノ基、エポキシ官能性有機基、
ヒドロキシ基から選択される有機官能基を有する脂肪族
不飽和炭化水素化合物またはこれらの有機官能基の活性
水素がトリオルガノシリル基で置換された脂肪族不飽和
炭化水素化合物（以下 化合物（III）と総称する。）と
しては、以下の化合物が挙げられる。In the present invention, the organosilicon compound (II)
Amino groups, epoxy-functional organic groups,
An aliphatic unsaturated hydrocarbon compound having an organic functional group selected from a hydroxy group or an aliphatic unsaturated hydrocarbon compound in which active hydrogen of these organic functional groups is substituted with a triorganosilyl group (hereinafter referred to as compound (III); The following compounds may be mentioned as generic names.
【化２１】 Embedded image
【化２２】 Embedded image
【化２３】 Embedded image
【化２４】 Embedded image
【化２５】 Embedded image
【化２６】 Embedded image
【化２７】 Embedded image
【化２８】 Embedded image
【化２９】 Embedded image
【化３０】 Embedded image
【化３１】 Embedded image
【０００８】有機ケイ素化合物（II）と化合物（III）
との反応で使用される触媒は、ヒドロシリル化反応に使
用されるものである。具体的には、塩化白金酸、塩化白
金酸のアルコール溶液、白金とオレフィンの錯体、白金
とビニルシロキサンの錯体等の白金系触媒；ウィルキン
ソン錯体、ロジウムとカルボニルの錯体等のロジウム系
触媒等が例示される。このヒドロシリル化反応で使用さ
れる触媒の使用量は、有機ケイ素化合物（II）と化合物
（III）の総量１００万重量部に対して、触媒原子として
１〜１００重量部の範囲内の量であり、好ましくは１〜
５０重量部の量である。これは触媒の添加量が、有機ケ
イ素化合物（II）と化合物（III）の総量１００万重量
部に対して、触媒原子として１重量部未満であると付加
反応が進行しない場合もあり、また１００重量部を越え
ても、付加反応速度がその使用量に比例して促進される
ことはなく、このような高価な触媒を多量に使用するこ
とは、不経済だからである。[0008] Organosilicon compounds (II) and compounds (III)
The catalyst used in the reaction with is the one used in the hydrosilylation reaction. Specific examples include platinum-based catalysts such as chloroplatinic acid, alcohol solutions of chloroplatinic acid, complexes of platinum and olefins, and complexes of platinum and vinylsiloxane; and rhodium-based catalysts such as Wilkinson complexes and complexes of rhodium and carbonyl. Is done. The amount of the catalyst used in this hydrosilylation reaction is in the range of 1 to 100 parts by weight as a catalyst atom based on 1 million parts by weight of the total amount of the organosilicon compound (II) and the compound (III). , Preferably 1 to
The amount is 50 parts by weight. If the amount of the catalyst is less than 1 part by weight as a catalyst atom with respect to 1 million parts by weight of the total amount of the organosilicon compound (II) and the compound (III), the addition reaction may not proceed. Even if the amount exceeds the parts by weight, the addition reaction rate is not accelerated in proportion to the amount used, and it is uneconomical to use a large amount of such an expensive catalyst.
【０００９】この付加反応温度は特に限定されないが、
通常、２５〜２５０℃の範囲内であり、好ましくは５０
〜２００℃の範囲である。これは反応温度が２５℃未満
であると反応速度が遅く生産性が低下し、また反応温度
が２５０℃を越えると付加反応触媒によって引き起こさ
れる副反応が起こる恐れがあるためである。The addition reaction temperature is not particularly limited,
Usually it is in the range of 25-250 ° C, preferably 50
~ 200 ° C. This is because if the reaction temperature is lower than 25 ° C., the reaction rate is low and the productivity is lowered, and if the reaction temperature is higher than 250 ° C., a side reaction caused by the addition reaction catalyst may occur.
【００１０】尚、この付加反応時に、有機溶媒を使用す
ることは本発明の目的を損わない限り任意である。この
ような有機溶媒としては、ベンゼン、トルエン、キシレ
ン等芳香族系溶媒、ヘキサン、ヘプタン等の脂肪族系溶
媒、テトラヒドロフラン、ジエチルエーテル等のエーテ
ル系溶媒、アセトン、メチルエチルケトン等のケトン系
溶媒、酢酸エチル、酢酸ブチル等のエステル系溶媒等が
ある。The use of an organic solvent during the addition reaction is optional as long as the object of the present invention is not impaired. Examples of such organic solvents include aromatic solvents such as benzene, toluene, and xylene; aliphatic solvents such as hexane and heptane; ether solvents such as tetrahydrofuran and diethyl ether; ketone solvents such as acetone and methyl ethyl ketone; and ethyl acetate. And ester solvents such as butyl acetate.
【００１１】ここで重要なことは、有機ケイ素化合物
（II）中のケイ素原子結合水素原子と等モル以上の化合
物（III）を付加反応に用いることである。付加反応終
了後、反応混合物から蒸留によって未反応の化合物（II
I）を減圧留去することにより、目的とする有機ケイ素
化合物（I）を得ることができる。What is important here is that the compound (III) having an equimolar amount or more with respect to the silicon-bonded hydrogen atom in the organosilicon compound (II) is used for the addition reaction. After completion of the addition reaction, the unreacted compound (II
The desired organosilicon compound (I) can be obtained by distilling off I) under reduced pressure.
【００１２】本発明の有機ケイ素化合物は、一分子中に
２個以上のケイ素原子結合有機官能基とケイ素原子結合
加水分解性基を有しており、ポリイミド樹脂等の各種有
機樹脂の改質剤として有用であり、また各種有機樹脂と
無機物質を接着させるための接着剤あるいはプライマー
として有用である。The organosilicon compound of the present invention has two or more silicon-bonded organic functional groups and silicon-bonded hydrolyzable groups in one molecule, and is used as a modifier for various organic resins such as polyimide resins. It is also useful as an adhesive or a primer for bonding various organic resins and inorganic substances.
【００１３】[0013]
【実施例】以下、実施例にて、本発明をより詳細に説明
する。実施例中、Ｍｅはメチル基を表す。The present invention will be described in more detail with reference to the following examples. In the examples, Me represents a methyl group.
【００１４】[0014]
【実施例１】攪拌器、還流冷却管、滴下ロート、温度計
を備えた四つ口フラスコに、次式で示される化合物１０
８.７グラム（０.２６１モル）と、塩化白金酸と１,３
−ジビニル−１,１,３,３−テトラメチルジシロキサン
とより調製した、白金ビニルシロキサン錯体（白金濃度
４.６重量パーセント）４７.３ミリグラムを入れた。Example 1 In a four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, a compound 10 represented by the following formula was placed.
8.7 grams (0.261 moles) of chloroplatinic acid and 1.3
47.3 milligrams of a platinum vinyl siloxane complex (4.6 weight percent platinum concentration) prepared from divinyl-1,1,3,3-tetramethyldisiloxane.
【化３２】 これらの混合物を９０℃まで加熱し、そこにＮ−トリメ
チルシリルアリルアミン８０.９グラム（０.６２６モ
ル）を１.２時間かけて滴下した。 滴下終了後、９０〜
１７０℃で３.５時間反応させた。 反応混合物から低沸
点物質を１９０℃／３ｍｍＨｇで３時間減圧留去し、
次式で示される化合物（Ａ）を１５５.８グラム得た。
この化合物の収率は８９％であった。Embedded image The mixture was heated to 90 ° C., and 80.9 g (0.626 mol) of N-trimethylsilylallylamine was added dropwise over 1.2 hours. 90-
The reaction was carried out at 170 ° C. for 3.5 hours. Low-boiling substances were distilled off from the reaction mixture under reduced pressure at 190 ° C./3 mmHg for 3 hours.
155.8 g of a compound (A) represented by the following formula was obtained.
The yield of this compound was 89%.
【化３３】 Embedded image
【００１５】[0015]
【実施例２】攪拌器、還流冷却管、滴下ロート、温度計
を備えた四つ口フラスコに、次式で示される化合物６
８.６グラム（０.０９６２モル）と、塩化白金酸と１,
３−ジビニル−１,１,３,３−テトラメチルジシロキサ
ンとより調製した、白金ビニルシロキサン錯体（白金濃
度４.６重量パーセント）１５.０ミリグラムを入れた。Example 2 A four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer was charged with a compound 6 represented by the following formula.
8.6 grams (0.0962 moles) of chloroplatinic acid and 1,
15.0 milligrams of a platinum vinyl siloxane complex (4.6 weight percent platinum concentration) prepared from 3-divinyl-1,1,3,3-tetramethyldisiloxane was charged.
【化３４】 これらの混合物を１０５℃まで加熱し、そこにＮ−トリ
メチルシリルアリルアミン３１.２グラム（０.２４１モ
ル）を５０分間かけて滴下した。滴下終了後、１２０〜
１６４℃で２時間反応させた。反応混合物から低沸点物
質を１３０℃／２ｍｍＨｇで３時間減圧留去し、次式で
示される化合物（Ｂ）を８９.０グラム得た。この化合
物の収率は９６％であった。Embedded image The mixture was heated to 105 ° C., and 31.2 g (0.241 mol) of N-trimethylsilylallylamine was added dropwise over 50 minutes. After dropping, 120 ~
The reaction was performed at 164 ° C. for 2 hours. Low-boiling substances were distilled off from the reaction mixture under reduced pressure at 130 ° C./2 mmHg for 3 hours to obtain 89.0 g of a compound (B) represented by the following formula. The yield of this compound was 96%.
【化３５】 Embedded image
【００１６】[0016]
【実施例３】攪拌器、還流冷却管、滴下ロート、温度計
を備えた四つ口フラスコに、次式で示される化合物１
０.１グラム（０.０２４２モル）と、塩化白金酸と１,
３−ジビニル−１,１,３,３−テトラメチルジシロキサ
ンとより調製した、白金ビニルシロキサン錯体のｉ−プ
ロパノール溶液（白金濃度４.７重量パーセント）７.０
ミリグラムを入れた。Example 3 A compound 1 represented by the following formula was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer.
0.1 g (0.0242 mol) of chloroplatinic acid and 1,
A solution of platinum vinyl siloxane complex in i-propanol (platinum concentration 4.7% by weight) 7.0 prepared from 3-divinyl-1,1,3,3-tetramethyldisiloxane 7.0
Milligrams were put.
【化３６】 これらの混合物を８５℃まで加熱し、そこにアリルグリ
シジルエーテル６.９１グラム（０.０６０５モル）を１
０分間かけて滴下した。 滴下終了後、８５〜１１０℃
で１.５時間反応させた。 反応混合物から低沸点物質を
１４０℃／３０ｍｍＨｇで１時間、次いで１８０℃／２
ｍｍＨｇで１時間減圧留去し、次式で示される化合物
（Ｃ）を１４.５グラム得た。この化合物の収率は９３
％であった。Embedded image The mixture was heated to 85 ° C. and 6.91 grams (0.0605 mole) of allyl glycidyl ether was added thereto.
It was added dropwise over 0 minutes. After dropping, 85-110 ° C
For 1.5 hours. Low-boiling substances were removed from the reaction mixture at 140 ° C./30 mmHg for 1 hour, then at 180 ° C./2
The residue was distilled under reduced pressure at 1 mmHg for 1 hour to obtain 14.5 g of a compound (C) represented by the following formula. The yield of this compound is 93
%Met.
【化３７】 Embedded image
【００１７】[0017]
【実施例４】攪拌器、還流冷却管、滴下ロート、温度計
を備えた四つ口フラスコに、次式で示される化合物１
２.０グラム（０.０２８８モル）と、塩化白金酸と１,
３−ジビニル−１,１,３,３−テトラメチルジシロキサ
ンとより調製した、白金ビニルシロキサン錯体のｉ−プ
ロパノール溶液（白金濃度４.７重量パーセント）７.０
ミリグラムを入れた。Example 4 A compound 1 represented by the following formula was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer.
2.0 grams (0.0288 mole) of chloroplatinic acid and 1,
A solution of platinum vinyl siloxane complex in i-propanol (platinum concentration 4.7% by weight) 7.0 prepared from 3-divinyl-1,1,3,3-tetramethyldisiloxane 7.0
Milligrams were put.
【化３８】 これらの混合物を１００℃まで加熱し、そこにアリルト
リメチルシリルエーテル９.３８グラム（０.０７２０モ
ル）を１０分間かけて滴下した。滴下終了後、１００〜
１２０℃で１時間反応させた。反応混合物から低沸点物
質を１００℃／２８ｍｍＨｇで１時間、次いで１４０℃
／２ｍｍＨｇで１時間減圧留去し、次式で示される化合
物（Ｄ）を１８.４グラム得た。 この化合物の収率は９
４％であった。Embedded image The mixture was heated to 100 ° C., and 9.38 g (0.0720 mol) of allyltrimethylsilyl ether was added dropwise thereto over 10 minutes. After dropping, 100 ~
The reaction was performed at 120 ° C. for 1 hour. Low boiling substances were removed from the reaction mixture at 100 ° C./28 mmHg for 1 hour, then at 140 ° C.
The residue was distilled under reduced pressure at / 2 mmHg for 1 hour to obtain 18.4 g of a compound (D) represented by the following formula. The yield of this compound is 9
4%.
【化３９】 Embedded image
【００１８】[0018]
【応用例１】攪拌器、還流冷却管、滴下ロート、温度計
を備えた四つ口フラスコに、二無水ピロメリット酸３.
９グラム（１７.９ミリモル）、無水フタル酸０.４１グ
ラム（２.７５ミリモル）、Ｎ−メチル−２−ピロリジ
ノン（以下ＮＭＰと略す。） ６８.６グラムを入れ
て、完全に溶解させた。そこに、実施例２で得られた化
合物（Ｂ）１８.８グラム（１９.３ミリモル）とＮＭＰ
１８.６グラムの混合物を２０分間かけて滴下した。滴
下終了後、室温で１.５時間反応させた。得られたポリ
アミック酸ＮＭＰ溶液をガラスプレートに塗布し、オー
ブン中で２００℃、３時間加熱したところ、黄色のポリ
イミド樹脂が得られた。このポリイミド樹脂は、ガラス
プレートに対し優れた接着性を示した。[Application Example 1] In a four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, add pyromellitic dianhydride to a four-necked flask.
9 g (17.9 mmol), 0.41 g (2.75 mmol) of phthalic anhydride, and 68.6 g of N-methyl-2-pyrrolidinone (hereinafter abbreviated as NMP) were added and completely dissolved. . There, 18.8 g (19.3 mmol) of the compound (B) obtained in Example 2 and NMP
18.6 grams of the mixture was added dropwise over 20 minutes. After the completion of the dropwise addition, the reaction was carried out at room temperature for 1.5 hours. The resulting polyamic acid NMP solution was applied to a glass plate and heated in an oven at 200 ° C. for 3 hours to obtain a yellow polyimide resin. This polyimide resin showed excellent adhesion to a glass plate.
【００１９】[0019]
【発明の効果】本発明の有機ケイ素化合物は、新規な有
機ケイ素化合物であり、またその製造方法はかかる新規
な有機ケイ素化合物を生産性よく製造できるという特徴
を有する。The organosilicon compound of the present invention is a novel organosilicon compound, and its production method is characterized in that such a novel organosilicon compound can be produced with high productivity.
【図１】図１は実施例１で製造した有機ケイ素化合物
（Ａ）の赤外線吸収スペクトルチャートである。FIG. 1 is an infrared absorption spectrum chart of the organosilicon compound (A) produced in Example 1.
【図２】図２は実施例２で製造した有機ケイ素化合物
（Ｂ）の赤外線吸収スペクトルチャートである。FIG. 2 is an infrared absorption spectrum chart of the organosilicon compound (B) produced in Example 2.
【図３】図３は実施例３で製造した有機ケイ素化合物
（Ｃ）の赤外線吸収スペクトルチャートである。FIG. 3 is an infrared absorption spectrum chart of the organosilicon compound (C) produced in Example 3.
【図４】図４は実施例４で製造した有機ケイ素化合物
（Ｄ）の赤外線吸収スペクトルチャートである。FIG. 4 is an infrared absorption spectrum chart of the organosilicon compound (D) produced in Example 4.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C08G 77/50 C08G 77/04 ──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. 7 , DB name) C08G 77/50 C08G 77/04
Claims (2)
異種の一価炭化水素基、Ｒ2は二価炭化水素基、 Ａはア
ミノ基、エポキシ官能性有機基、ヒドロキシ基から選択
される有機官能基またはこれらの官能基の活性水素がト
リオルガノシリル基で置換された有機官能基、Ｘは加水
分解性基、ｎは０または１の整数、ｍは０から１００ま
での整数、ｐは０または１の整数を示す。）で表される
有機ケイ素化合物（I）。(1) A general formula: (Wherein, R 1 is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, R 2 is a divalent hydrocarbon group, and A is an amino group, an epoxy-functional organic group, or a hydroxy group. An organic functional group or an organic functional group in which active hydrogens of these functional groups are substituted with a triorganosilyl group, X is a hydrolyzable group, n is an integer of 0 or 1, m is an integer of 0 to 100, p Represents an integer of 0 or 1.).
る。）で表される有機ケイ素化合物（II）と、アミノ
基、エポキシ官能性有機基、ヒドロキシ基から選択され
る有機官能基を含有する脂肪族不飽和炭化水素化合物ま
たはこれらの有機官能基の活性水素がトリオルガノシリ
ル基で置換された脂肪族不飽和炭化水素化合物とを付加
反応させることを特徴とする、一般式： 【化３】 （式中、Ｒ1、Ｒ2、Ａ、Ｘ、ｎ、ｍ、ｐは前記に同じで
ある。）で表される有機ケイ素化合物（I）の製造方
法。2. A compound of the general formula: (Wherein, R 1 , R 2 , X, n, m, and p are the same as described above), and an amino group, an epoxy-functional organic group, or a hydroxy group. Characterized in that an addition reaction of an aliphatic unsaturated hydrocarbon compound containing an organic functional group to be performed or an aliphatic unsaturated hydrocarbon compound in which active hydrogen of these organic functional groups is substituted with a triorganosilyl group is performed. , The general formula: (Wherein, R 1 , R 2 , A, X, n, m, and p are the same as described above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23553291A JP3193740B2 (en) | 1991-08-22 | 1991-08-22 | Organosilicon compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23553291A JP3193740B2 (en) | 1991-08-22 | 1991-08-22 | Organosilicon compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0551462A JPH0551462A (en) | 1993-03-02 |
| JP3193740B2 true JP3193740B2 (en) | 2001-07-30 |
Family
ID=16987373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23553291A Expired - Fee Related JP3193740B2 (en) | 1991-08-22 | 1991-08-22 | Organosilicon compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3193740B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0834852A (en) | 1994-07-21 | 1996-02-06 | Toray Dow Corning Silicone Co Ltd | Silicone-modified polyamide solution composition |
-
1991
- 1991-08-22 JP JP23553291A patent/JP3193740B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0551462A (en) | 1993-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3224830B2 (en) | Organosilicon compound and method for producing the same | |
| US6911518B2 (en) | Polyhedral oligomeric -silsesquioxanes, -silicates and -siloxanes bearing ring-strained olefinic functionalities | |
| EP0112845B1 (en) | Method for making silylnorbornane anhydrides | |
| JPH0583569B2 (en) | ||
| JP2008512546A (en) | Anhydride functional silsesquioxane resin | |
| US6455640B2 (en) | Method for producing basic amino acid-modified organopolysiloxane | |
| JP2000239390A (en) | Carbosiloxane dendrimer | |
| US20060041098A1 (en) | Synthesis and characterization of novel cyclosiloxanes and their self- and co-condensation with silanol-terminated polydimethylsiloxane | |
| JP4079314B2 (en) | Method for producing silsesquioxane compound | |
| JP3193740B2 (en) | Organosilicon compound and method for producing the same | |
| US6172252B1 (en) | Pheno-functional organosilicon compounds and method for the preparation | |
| EP0586241B1 (en) | Azasilacycloalkyl functional alkoxysilanes and azasilacycloalkyl functional tetramethyldisiloxanes | |
| JP3012358B2 (en) | Heat-curable epoxy resin composition | |
| JP2002088157A (en) | Ladder type silsesquioxane compound containing styryl group as substituent group and method for producing the same | |
| JP2000044579A (en) | Carbosiloxane dendrimer | |
| US6555644B2 (en) | Multi-reactive silicon compound having polyalkyleneglycol substituents and synthetic method thereof | |
| JPH04128292A (en) | Method for producing γ-methacryloxypropylsilane compound | |
| JPH0493326A (en) | Method for producing alkoxy-functional organopolysiloxane | |
| JPH08325381A (en) | Organosilicon compound and its production | |
| JP3819087B2 (en) | New silane coupling agent | |
| JP3212248B2 (en) | Method for producing acryloxy group-containing organopolysiloxane | |
| JPH06136129A (en) | Organopolysiloxane and its production | |
| JP2002097273A (en) | Organopolysiloxane and method of producing the same | |
| TW202436309A (en) | Composition containing aminoalkyl alkoxy disiloxane compound and aminoalkyl alkoxy oligosiloxane compound and preparation method thereof | |
| JPH03184983A (en) | Amino group-containing silane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |